JP5277319B2 - Organic EL device and manufacturing method thereof - Google Patents

Description

  The present invention relates to an organic EL element and a method for manufacturing the same.

  An organic EL (electroluminescence) element has a structure in which an organic functional layer including a light emitting layer is sandwiched between an anode and a cathode. When a voltage is applied in this configuration, holes and electrons injected from the anode and the cathode into the light emitting layer recombine and self-emit light.

  An organic EL element is generally an element having low resistance to oxygen and moisture in the atmosphere, and as a typical deterioration, there is a phenomenon in which a non-light emitting portion called a dark spot is generated and expanded in a light emitting region. Although there are various theories regarding the mechanism of dark spots, it is considered that one reason is that the injection of electrons from the cathode into the adjacent organic layer is hindered by oxygen, moisture, or the like entering the device.

As a material for the cathode, a material having a low work function such as Mg: Ag, Li: Al, Ca, Li ₂ O / Al, or the like is used in order to improve electron injection. For this reason, the cathode is easily oxidized by oxygen and moisture in the atmosphere. For example, when Al is used, AlOx is formed, and depending on the material, an insulating oxide film is formed. The dark spot is generated because the cathode at the site where oxidation has deteriorated loses the function of injecting electrons, and the interface resistance locally increases.

  Conventionally, as one of the countermeasures for suppressing the oxidation of the cathode, a film that forms a thin film of a material having low oxygen and moisture transmittance, such as silicon nitride (SiNx), and seals the element A sealing structure is used. However, even if such a film sealing structure is used, it is difficult to completely prevent the dark spots from being generated and enlarged due to the intrusion of oxygen and moisture from defective portions such as pinholes and cracks. In particular, one of the features of the organic EL element is that it can be formed on a flexible substrate such as a plastic, and there is a problem that cracks are likely to occur when bent.

  Here, in a conventional organic EL device, a structure having a hole-electron current conversion layer in which an electron transport layer and a hole transport layer are stacked with a thermally reducible metal layer interposed is known (for example, a patent) Reference 1). The hole-electron current conversion layer is disposed for the purpose of efficiently converting the hole current into an electron current. However, heat-reducible metals such as aluminum are easily oxidized like the cathode, and when an oxide film is formed, the hole-electron current conversion efficiency is lowered. In addition, as can be seen from the results of FIGS. 8 and 9 of Patent Document 1, light emission itself does not occur unless a heat-reducible metal is present. As described above, the heat-reducible metal is an indispensable element for the organic EL element having the structure disclosed in Patent Document 1. Therefore, the generation of dark spots due to oxidation of not only the cathode but also the thermally reducible metal becomes a problem.

  Further, the organic EL element of Patent Document 1 also has a problem that when a cathode formed of a material having a low work function such as Li is oxidized, a charge transfer complex necessary for the element to emit light is not formed.

Japanese Patent No. 4243237

  That is, the above-described problem is given as an example of the problem to be solved by the present invention. Therefore, an object of the present invention is to provide an organic EL element that has resistance to moisture and oxygen and that can suppress the occurrence and expansion of non-light emitting portions such as dark spots, and a method for manufacturing the same.

  Another example of the present invention is to provide an organic EL element that can suppress the oxidation of the electrode even when moisture or oxygen enters the element and a method for manufacturing the same.

The organic EL element of the present invention is an organic EL element in which an organic functional layer including at least one light emitting layer is disposed between a first electrode and a second electrode as described in claim 1, includes a bipolar charge generation layer in which the organic functional layer to generate electrons and holes, the one electrode of the first electrode and the second electrode Ri der Hall-receiving electrode, the bipolar charge generation layer, bipolar by oxygen It characterized that you have been formed of a material containing an organic semiconductor that has changed sex.

The method for producing an organic EL device according to the present invention produces an organic EL device in which an organic functional layer including at least one light emitting layer is disposed between the first electrode and the second electrode, as described in claim 10. And forming one of the first and second electrodes as a hole receiving electrode by forming a bipolar charge generation layer for generating electrons and holes in one of the layers constituting the organic functional layer. The material for forming the bipolar charge generation layer includes an organic semiconductor that changes to bipolar by oxygen, and after forming a film under vacuum using the material, the material is exposed to a gas containing oxygen, or oxygen is An ambipolar charge generation layer is formed by supplying a gas containing the liquid .

It is a longitudinal cross-sectional view of the organic EL element by 1st Embodiment of this invention. It is a figure for demonstrating the bipolar charge generation layer of the said organic EL element. It is the figure which showed typically the hole of the said organic EL element, and the flow of an electron. It is the image data which image | photographed the light emission state when the said organic EL element was exposed to air | atmosphere. It is the image data which image | photographed the light emission state when the organic EL element of a conventional structure was exposed to air | atmosphere. It is a flowchart which shows the preferable manufacturing process of the said organic EL element. It is a longitudinal cross-sectional view of the organic EL element by 3rd Embodiment of this invention. It is a longitudinal cross-sectional view of the organic EL element by 4th Embodiment of this invention. It is the image data which image | photographed the light emission state when the organic EL element of Example 2 according to the said 4th Embodiment was exposed to air | atmosphere.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Organic functional layer 31 Light emitting layer 32 Bipolar charge generation layer 33 Hole injection layer 34 Hole transport layer 35 Charge generation promotion layer 35 Charge generation promotion layer 4 Hole receiving electrode

  Hereinafter, an organic EL device and a manufacturing method thereof according to preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical scope of the present invention is not construed as being limited by the embodiments described below.

(First embodiment)
As shown in FIG. 1, the organic EL device according to the present embodiment functions on a substrate 1 as a first electrode 2 that functions as an anode, an organic functional layer 3 that includes at least one light emitting layer 31, and a hole receiving electrode. The second electrode 4 is laminated. The structure in which the organic functional layer 3 is disposed between the first electrode 2 and the second electrode 4 is the same as the conventional structure. However, in this embodiment, the organic functional layer is arranged so that the bipolar charge generation layer 32 that generates electrons and holes when a bias voltage is applied is positioned between the light emitting layer 31 and the second electrode 4. The second electrode 4 is not a conventional electron injection type electrode (cathode) but a hole receiving electrode that receives holes from the light emitting layer 31.

  As long as the organic functional layer 3 has at least the light emitting layer 31 and the ambipolar charge generation layer 32, the layer structure itself is not particularly limited and can be appropriately changed. For example, functional layers such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a carrier block layer are arranged in order to increase the light emission efficiency by promoting the electroluminescence phenomenon or according to the use of the device. be able to. In this case, each layer may have a single layer structure or a stacked structure including a plurality of layers formed with different materials. Furthermore, an inorganic material may be contained in the layer, or a layer made of an inorganic material may be included in the laminated structure. FIG. 1 shows, as an example, an organic functional layer 3 in which a hole injection layer 33, a hole transport layer 34, a light emitting layer 31, and an ambipolar charge generation layer 32 are stacked in this order from the anode 2 side.

  The bipolar charge generation layer 32 is formed of a bipolar material that generates electrons and holes when a bias voltage is applied. An example of such a material is a bipolar organic semiconductor. The layer may contain a material other than bipolar. Here, the bipolar organic semiconductor means an organic semiconductor that can be driven by n-channel or p-channel such as MOS-FET. That is, it can be paraphrased as a material that can generate electrons and holes by applying an electric field, or a material that easily generates electrons and holes. Even in a state where an electric field is not applied, as in a depletion type FET, an organic semiconductor in which one or both charges are present may be used.

  The bipolar charge generation layer 32 only needs to contain a material having both polarities, and the material forming the layer is not limited. However, as schematically shown in FIG. 2, it is desirable that the difference between the ionization potential and the electron affinity, that is, the Ip-Ea gap (HOMO-LUMO gap) is made of a narrow material. This is because if the Ip-Ea gap (HOMO-LUMO gap) is narrow, the triangular potential at the time of electric field application can be reduced, the tunnel effect easily occurs, and electrons and holes are generated. More specifically, it is desirable that the Ip-Ea gap is 2.5 eV or less.

Furthermore, the ambipolar charge generation layer 32 may be a mixed layer made of a plurality of materials. As a specific example, a mixed layer of CuPc and F16CuPc, mixed layer of CuPc and _{C 60,} a mixed layer of pentacene and F16CuPc, and the like mixed layer of pentacene and perfluoropentacene. It may not be a mixed layer of an organic material and an organic material, and may be a mixed layer of an organic material and an inorganic material. However, it is not preferable to have a structure in which films made of the respective materials are laminated. This is because the depletion region becomes wider and the tunnel effect does not occur, and generation of electrons and holes is insufficient or may not be generated. Control of the depletion region is important in arranging the bipolar layer. In the structure of the organic EL element disclosed in Patent Document 1, if the thermally reducible metal layer that is unstable in the atmosphere is omitted from the hole-electron current conversion layer, the depletion region becomes wide, and the low work function metal is doped. Electrons are hardly generated in the electron transporting portion, which is a formed layer (generally an N-doped layer) (that is, it is difficult to form a charge transfer complex in the N-doped layer), and light emission does not occur.

Therefore, in this embodiment, each material is a mixed layer dispersed in the layer. Such a mixed layer is preferably formed by, for example, co-evaporation. _{That, CuPc: F16CuPc, CuPc: C} 60, pentacene: F16CuPc, pentacene: perfluoropentacene the like. The film may be dissolved or dispersed in a solvent and formed by a coating method. Even when the ambipolar charge generation layer 32 is formed of a mixed layer composed of a plurality of organic semiconductors, the difference between the smallest Ip and the largest Ea among the mixed organic semiconductors is 2.5 eV or less. Is more desirable.

  In addition, as a material for forming the bipolar charge generation layer 32, for example, an organic semiconductor that changes to bipolar by atmospheric oxygen can be used. Specific examples of organic semiconductors that change to bipolar by oxygen include fullerenes (LUMO = 4.4 eV, HOMO = 6.3 eV), or fullerene derivatives (reference: A. Tapponier, et. Al Appl. Phys. Lett. 86, 112114 (2005)), TiOPc (LUMO = 3.8 eV, HOMO = 5.2 eV) (reference: H. Tada, et. Al Appl. Phys. Lett. 76, 873 (2000)). It is done. Since these materials are hardly soluble in a solvent, the film is not usually formed by a coating method but is formed by vacuum deposition. Therefore, after forming a film under vacuum, it can be exposed to a gas containing oxygen, or a gas containing oxygen can be supplied to change the polarity. For example, it can be changed to bipolar by exposure to the atmosphere.

  The preferred film thickness of the ambipolar charge generation layer 32 is influenced by the Ip-Ea gap and the HOMO and LUMO of the adjacent functional layer (the light emitting layer 31 in the case of FIG. 1), so that the amount of charge generation is affected. It is appropriately adjusted according to the charge balance of the element. In order to function as the bipolar charge generation layer 32, at least 1 nm is required. However, since the resistance value increases and the drive voltage increases as the film thickness increases, the thickness is preferably 100 nm or less.

  Since the hole receiving electrode 4 does not inject electrons as in the conventional cathode, but receives holes generated in the bipolar charge generation layer 32, the work function is preferably 4.0 eV or more. More preferably, the material has a large Ip for receiving holes from the ambipolar charge generation layer 32 and is stable in the atmosphere. Specifically, Au, Pt, etc. that are stable in the air, Ag, Cr, Mo, etc. that do not become insulating even when oxidized, or materials that are stable in the air atmosphere by an alloy, for example, Al: Nd, Examples thereof include conductive oxides such as Ti: Al, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SnOx. These are materials having a high work function (Wf) that cannot be used for conventional electron injection type electrodes (cathodes). In the case of a top emission structure in which light emission is extracted from the hole receiving electrode 4 side, a transparent material such as ITO or IZO is used. For example, in the case of a microcavity structure that uses the resonance effect, a material that is not transparent but reflective is used. Although not shown in FIG. 1, a lead electrode (wiring electrode) for applying a bias voltage is connected to the hole receiving electrode 4.

  The material of the substrate 1 is not particularly limited as long as an element can be formed on the surface thereof. Examples of the substrate 1 include a glass substrate, a metal substrate, and a resin substrate such as plastic. As will be described later, the organic EL element according to the present embodiment can suppress the generation and expansion of the non-light emitting portion due to oxygen or moisture in the atmosphere even if a defect portion such as a crack occurs in the sealing film. Therefore, it can be said that the above-mentioned effect is most exhibited when a flexible substrate that easily causes cracks or the like in the sealing film is used.

  The anode 2 is made of a material having a high work function so that holes can be injected into the adjacent hole injection layer 33. Specifically, for example, a metal such as Cr, Mo, Ni, Pt, or Au, a compound thereof, or an alloy containing them can be used. In the case of a bottom emission structure in which light emission is extracted from the substrate 1 side, a transparent conductive oxide such as ITO or IZO is used. The thickness of the anode 2 is not particularly limited. Although not shown in FIG. 1, a lead electrode (wiring electrode) for applying a bias voltage is connected to the anode 2.

Examples of the light emitting layer 31 include fluorescent organometallic compounds such as tris (8-hydroxyquinolinate) aluminum complex (Alq ₃ ), 4,4′-bis (2,2′-diphenylvinyl) -biphenyl (DPVBi), and the like. Aromatic dimethylidin compounds, styrylbenzene compounds such as 1,4-bis (2-methylstyryl) benzene, 3- (4-biphenyl) -4-phenyl-5-t-butylphenyl-1,2,4-triazole Fluorescent organic materials such as triazole derivatives such as (TAZ), anthraquinone derivatives and fluorenol derivatives, polymer materials such as polyparafinylene vinylene (PPV), polyfluorene and polyvinylcarbazole (PVK), platinum complexes and iridium complexes A phosphorescent organic material such as can be used. However, it is not limited to these materials.

  The hole injection layer 33 and the hole transport layer 34 may be formed of a material having a high hole transport property. As an example, a phthalocyanine compound such as copper phthalocyanine (CuPc), a starburst amine such as m-MTDATA, Benzidine-type amine multimers, aromatic thirds such as 4,4′-bis [N- (1-naphthyl) -N-phenylamino] -biphenyl (NPB), N-phenyl-p-phenylenediamine (PPD) Materials such as primary amines, stilbene compounds such as 4- (di-P-tolylamino) -4 ′-[4- (di-P-tolylamino) styryl] stilbenzene, triazole derivatives, and styrylamine compounds are used. Further, a polymer dispersion material in which a low molecular material is dispersed in a polymer material such as polycarbonate may be used. However, it is not limited to these materials

The electron injection layer and the electron transport layer may be formed of a material having a high electron transport property. Examples thereof include silacyclopentadiene (silole) derivatives such as PyPySPyPy, nitro-substituted fluorenone derivatives, anthraquinodimethane derivatives, and the like. Organic materials, metal complexes of 8-quinolinol derivatives such as tris (8-hydroxyquinolinate) aluminum (Alq ₃ ), metal phthalocyanine, 3- (4-biphenyl) -5- (4-t-butylphenyl)- Triazole compounds such as 4-phenyl-1,2,4-triazole (TAZ), 2- (4-biphenylyl) -5- (4-t-butyl) -1,3,4-oxadiazol (PBD) An oxadiazole-based compound such as can be used. However, it is not limited to these materials.

  In the case of providing the sealing film, it can be formed of an inorganic material having a low water vapor or oxygen permeability, for example. As conventionally performed, for example, a film sealing structure formed by vapor deposition using silicon nitride (SiNx), silicon nitride oxide (SiOxNy), aluminum oxide (AlOx), aluminum nitride (AlNx), etc. I can do it. However, since the organic EL element of the present embodiment has atmospheric stability, the organic EL element does not have a strong sealing as in the prior art and can have a simple sealing structure. In this case, there is an advantage that the manufacturing cost can be reduced. Examples of simple sealing include a structure in which the sealing film is thinned, a solid sealing structure that does not use a sealing film (Japanese Patent Laid-Open No. 5-182759, etc.), and a polymer resin layer having a relatively large gas permeability. Examples include a structure protected by (epoxy resin or the like). Moreover, the hollow sealing which enclosed the small amount of desiccant may be sufficient.

  When a bias voltage is applied to the organic EL element having the above-described structure, holes are injected from the anode 2 into the hole injection layer 33 as schematically shown in FIG. 3, and holes are formed in the light emitting layer 31 through the adjacent hole transport layer 34. Is supplied. On the other hand, holes and electrons are generated in the bipolar charge generation layer 32 to which an electric field is applied. The generated holes are received by the hole receiving electrode 4, and the generated electrons are supplied to the light emitting layer 31. Light is emitted by recombination of holes and electrons in the light emitting layer 31.

The image data shown in FIG. 4 shows the light emission state of the element when a layer corresponding to the bipolar charge generation layer 32 is formed using fullerene, which is an organic semiconductor, and then the fullerene is changed to bipolar using oxygen. It is an example which image | photographed for the elapsed time shown in the figure. That is, fullerenes that normally have no polarity were formed into a film under vacuum and, for example, exposed to the atmosphere to change to bipolar. Specifically, after forming the anode 2, the hole injection layer 33, the hole transport layer 34, the light emitting layer 31, and the electron injection layer on the glass substrate 1, a fullerene film is formed by vapor deposition, for example, under vacuum, and further the hole The receiving electrode 4 is formed. Normally, this is sealed. Here, the element was placed in the atmosphere without forming a sealing film, and a bias voltage was applied. The materials of the anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / ambipolar charge generation layer / hole receiving electrode were ITO (110) / CuPc (25) / αNPD (45) / Alq ₃ (30 ) / Li ₂ O (1) / C ₆₀ (25) / Au (80). The value in parentheses is the film thickness (unit: nm). This test corresponds to Example 1 described later.

  As shown in FIG. 4, no light emission was obtained at the initial stage (0h) when the fullerene has not yet changed to bipolar. However, the light emitting region is generated and enlarged as time passes. This is because the upper surface of the bipolar charge generation layer 32 is covered with the Au electrode 4, but the side end surface is exposed to the air atmosphere because no sealing film is formed, so that oxygen penetrates from the side end surface. This is because fullerene gradually changed to bipolar. Then, when 500 hours passed, the entire light emitting region emitted light, and even after 2500 hours, oxidation deterioration of the electrode was suppressed and light emission continued. Since it continues to emit light up to 2500 hours without sealing, it can be expected that the lifetime is further extended by applying sealing. In addition, the said light emission area | region is an area | region where the anode 2, the light emitting layer 31, and the hole receiving electrode 4 have overlapped seeing from the surface which takes out light emission.

On the other hand, the image data shown in FIG. 5 is an example of a result obtained by fabricating an organic EL element having a conventional structure and conducting a similar atmospheric exposure test. That is, an organic EL device having a conventional structure was fabricated by laminating an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and a cathode in this order on a glass substrate. The element was placed in the atmosphere without forming a sealing film, and a bias voltage was applied. ITO / CuPc / αNPD / Alq ₃ / Li ₂ O / Al were used as materials for the anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, respectively.

  As shown in FIG. 5, the organic EL element having the conventional structure emits light entirely in the initial stage (0h), but dark spots are generated and enlarged as time passes. At the time of 2500 h, the entire surface is not emitting light. This is because the cathode (particularly, the interface with the electron injection layer) has deteriorated due to oxidation, and electrons cannot be injected.

  As is apparent from the results shown in FIGS. 4 and 5, the organic EL element using an organic semiconductor that changes in polarity by oxygen is completely opposite to conventional elements with respect to atmospheric oxygen and moisture. Shows the behavior. That is, in the conventional organic EL element, oxygen and moisture in the atmosphere are degradation factors that inhibit light emission, whereas in the organic EL element of the present embodiment, oxygen and moisture are active factors that promote light emission. .

  As described above, according to this embodiment, in the organic EL element in which the first electrode 2, the organic functional layer 3, and the second electrode 4 are stacked in this order, the ambipolar charge generation layer 32 that generates electrons and holes is emitted. Since the second electrode 4 is disposed between the layer 31 and the second electrode 4, the electrode function of the second electrode 4 can be changed from a conventional electron injection electrode to a hole receiving electrode. Thereby, the 2nd electrode 4 can be formed using a material with a high work function. In order to improve the hall receiving function, a material having a high work function is preferable. As a result, the resistance of the element to oxygen and moisture is increased, and generation and expansion of non-light emitting portions such as dark spots can be suppressed. That is, since both the first and second electrodes can be formed of a material having a high work function, resistance to oxygen and moisture can be increased.

  In particular, if a material having an electrode work function of 4.0 eV or more is selected, oxidation can be more reliably suppressed.

  In addition, according to the present embodiment, the bipolar charge generation layer 32 is formed using a bipolar material that generates electrons and holes when a bias voltage is applied, so that the bipolar charge generation layer 32 is a single layer. Can be formed. In particular, when an organic semiconductor that changes to bipolar by oxygen is used, oxygen can be an active factor that promotes light emission. This is an action that cannot be achieved with an organic EL element having a conventional structure. Here, for example, when organic EL elements that emit light in R (red), G (green), and B (blue) are arranged on a substrate to form a full-color display device, a partition wall that separates the elements is provided. May form. The partition wall can be used for separately coating the RGB elements by a coating method. Even in such a configuration, oxygen can be permeated and supplied by using a material having high gas permeability as the material of the partition wall, for example, a resist containing a fluorine component. Further, oxygen may be supplied from this portion as a structure in which a part of the end face of the bipolar charge generation layer 32 is exposed.

(Second Embodiment)
Next, an example of a method for manufacturing the organic EL element having the structure shown in FIG. 1 will be described with reference to FIG. However, as detailed, various materials can be applied to the organic EL element according to the present embodiment. Therefore, in the following, for convenience of explanation, an example will be described in which fullerene is used as the material of the bipolar charge generation layer 32 and the bipolar charge generation layer 32 is changed to bipolar by oxygen.

  As shown in FIG. 6, a glass substrate is used as the substrate 1, and an anode 2 (for example, ITO) is formed on the substrate 1 by a transparent material, for example, by vapor deposition or sputtering (process 100). The patterning of the electrode can be performed by, for example, a photolithography method. For example, in the case of the passive type, the electrodes are formed in a stripe shape, and in the case of the active type, for example, the electrodes 2 are formed in an island shape connected for each drive circuit.

  Next, a liquid material for the hole injection layer 33 is applied and dried to form a film (processing 110). The application method is not limited, but for example, an ink jet method can be employed. Similarly, the hole transport layer 34 is formed by a coating method. Further, the light emitting layer 31 is similarly formed by a coating method (processing 120). The film thickness can be adjusted by, for example, the amount of liquid material applied. Next, the bipolar charge generation layer 32 is formed under vacuum using, for example, a vapor deposition method (process 130). In the case where an electron injection layer is formed between the light emitting layer 31 and the ambipolar charge generation layer 32, it can be similarly formed by vapor deposition. Further, the hole receiving electrode 4 is formed using, for example, vapor deposition or sputtering (process 140). For patterning the hole receiving electrode 4, a mask such as a metal mask can be used. For example, in the case of the passive type, the hole receiving electrode 4 can be patterned in a stripe shape, and in the case of the active type, for example, the so-called solid electrode can be formed without patterning. Finally, the device is sealed as necessary, and an electric circuit is manufactured, thereby completing the organic EL device (processing 150).

  In addition, when forming the ambipolar charge generation layer 32 with a plurality of materials, it can be formed by, for example, a co-evaporation method. In the case where the bipolar charge generation layer 32 is formed of a material that changes to bipolar by oxygen, after forming the film up to the hole receiving electrode 4, the bipolar charge generation layer 32 is exposed to a gas containing oxygen (for example, the atmosphere). Change. Of course, before forming the hole receiving electrode 4, the hole receiving electrode 4 may be exposed to a gas containing oxygen to be changed into bipolar. Further, as a method of forming the bipolar charge generation layer 32, if an organic vapor phase deposition (OVPD) method is applied and oxygen is included in the carrier gas, oxygen is supplied while forming a film. Is possible.

(Third embodiment)
This embodiment is a modification of the first embodiment illustrated in FIG. That is, as shown in FIG. 7, the structure is the same as that illustrated in FIG. 1 except that a charge generation promoting layer 35 is disposed between the light emitting layer 31 and the ambipolar charge generation layer 32. The charge generation promoting layer 35 is disposed to promote charge generation in the bipolar charge generation layer 32. The charge generation promoting layer 35 can be formed, for example, by a vapor deposition method using a material such as LiF or MgF ₂ . The electron injection layer made of Li ₂ O exemplified in FIG. 4 and Example 1 also functions as the charge generation promoting layer 35. Even if it is such a structure, the effect similar to embodiment mentioned above can be acquired. Furthermore, by disposing the charge generation promoting layer 35 and increasing the film thickness between the first electrode 2 and the second electrode 4, defects such as a short circuit can be prevented.

(Fourth embodiment)
The present embodiment is a modified example in which the third embodiment shown in FIG. 7 is further modified. That is, as shown in FIG. 8, the structure is the same as that illustrated in FIG. 7 except that the second charge generation promoting layer 36 is disposed between the bipolar charge generation layer 32 and the hole receiving electrode 4. The second charge generation promoting layer 36 is also disposed in order to promote charge generation in the bipolar charge generation layer 32. Of course, the first charge generation promoting layer 35 may be omitted. The charge generation promoting layer 36 of this embodiment can be formed by using, for example, a material such as MoO ₃ , V ₂ O ₅ , or HAT-CN, for example, by vapor deposition. Even if it is such a structure, the effect similar to embodiment mentioned above can be acquired.

  In addition, although the 1st-4th embodiment mentioned above illustrated the structure which has arrange | positioned the light emitting layer 31 to the organic functional layer 3, it is not limited to this, The several light emitting layer 31 is not limited to this. It may be a structure in which is arranged. That is, a multi-photon structure in which a plurality of light-emitting units composed of the hole transport layer 34 / the light-emitting layer 31 / the electron transport layer, etc. are stacked may be used. Even if it is such a structure, the effect similar to the above-mentioned embodiment can be acquired.

  Further, the first to fourth embodiments described above have a structure in which the anode 2 is disposed on the substrate 1 side. However, the present invention is not limited to this, and the hole receiving electrode 4 is disposed on the substrate 1 side. Also good.

  The technology according to the above embodiment can be applied to organic devices such as organic EL displays, organic TFTs, and solar cells. In addition, the action of changing light to bipolar by oxygen to emit light may be applicable as an oxygen detector. However, the application is not limited.

  Although the present invention has been described in detail with reference to specific embodiments, various substitutions, modifications, changes, etc. in form and detail are defined in the claims. It will be apparent to those skilled in the art that this can be done without departing from the spirit and scope. Therefore, the scope of the present invention should not be limited to the above-described embodiments and the accompanying drawings, but should be determined based on the description of the claims and equivalents thereof.

<HTL / EML / Ambipolar charge generation layer / Hole receiving electrode>
An ITO anode 2 is formed on the glass substrate 1 by sputtering using a known technique, and CuPc is used as the hole injection layer 33, αNPD is used as the hole transport layer 34, Alq _{3 is used} as the light emitting layer 31, and electron injection is performed by vacuum deposition. Therefore, LiF was formed as the charge generation promoting layer 35, C ₆₀ was formed as the ambipolar charge generation layer 32, and Au was formed as the hole receiving electrode 4, thereby producing an organic EL element.

When left unsealed in the atmosphere (22 ° C., 50% RH), as shown in FIG. 4, only the region in which oxygen had entered began to emit light. As shown in Example 2, this mechanism was found to be due to oxygen entering the device from near the edge and C ₆₀ changing to bipolar. That is, oxygen in the invaded bipolar C ₆₀ region, the electrons in the Alq ₃ side of the lower than C _60, the upper Au side of C ₆₀ is considered to have been to generate holes. At this time, Au does not inject electrons but plays a role of receiving holes.

  Thereafter, the entire light emitting area of 2 mm × 2 mm began to shine in about 500 hours, and the conventional structure shown in FIG. 5 maintained a good light emitting state even at 1000 hours or more where the expansion of the non-light emitting area was significant. As mentioned above, the effect which suppresses expansion of a non-light-emitting part has been confirmed. Of course, further sealing time can be obtained by sealing.

<HTL / EML / Ambipolar charge generation layer / HTL / Hole receiving electrode>
In Example 2, it was carried out as a demonstration experiment that C ₆₀ into which oxygen actually entered was a bipolar charge generation layer and Au was the hole receiving electrode 4. An organic EL element in which αNPD as the charge generation promoting layer 36 was inserted between C _{60 of the} ambipolar charge generation layer 32 and Au serving as the hole receiving electrode 4 was produced. The αNPD of the charge generation promoting layer 36 has a structure in which electrons are not injected from Au because the electron transport property is poor. The manufacturing method was performed as follows.

An ITO anode 2 is formed on the glass substrate 1 by sputtering using a known technique, and CuPc is used as the hole injection layer 33, αNPD is used as the hole transport layer 34, Alq _{3 is used} as the light emitting layer 31, and electron injection is performed by vacuum deposition. LiF was formed as the charge generation promoting layer 35 for this purpose, C ₆₀ was used as the ambipolar charge generation layer 32, αNPD was formed as the charge generation promoting layer 36 for hole transport, and Au was formed as the hole receiving electrode 4, thereby producing an organic EL device. .

When left unsealed in the atmosphere (22 ° C., 50% RH), oxygen entered the device from the vicinity of the edge as shown in FIG. 9, and oxygen entered in the same manner as in Example 1. Only the area began to emit light. Since the αNPD of the charge generation promoting layer 36 has poor electron transport properties, electrons are not injected from Au, but Au is the hole receiving electrode 4, and C ₆₀ is the bipolar charge generation layer 32. It was shown that. The oxygen bipolar _{C 60} regions _invasion electrons to Alq ₃ side of the lower than _{C 60,} the upper side of the _{C 60} and to produce a hole, into Au hole-receiving electrode 4 via the αNPD propagation It is thought that.

  Thereafter, the entire light emitting area of 2 mm × 2 mm began to shine in about 500 hours, and in the conventional element, a good light emitting state was maintained even after 1000 hours when the non-light emitting area was significantly enlarged. As mentioned above, the effect which suppresses expansion of a non-light-emitting part has been confirmed. Of course, further sealing time can be obtained by sealing.

Claims (9)

An organic EL element in which an organic functional layer including at least one light emitting layer is disposed between a first electrode and a second electrode,
The organic functional layer includes an ambipolar charge generation layer for generating electrons and holes;
One of the first electrode and the second electrode is a hole receiving electrode, and the bipolar charge generation layer is formed between the hole receiving electrode and the light emitting layer,
The organic EL element is characterized in that the bipolar charge generation layer is formed of a material including an organic semiconductor in which a light emitting region is formed by changing from the end side to bipolar by oxygen contained in an atmosphere around the element. element. The other electrode of the first electrode and the second electrode is an anode;
2. The organic material according to claim 1, wherein the ambipolar charge generation layer is disposed between the light emitting layer and the hole receiving electrode and is formed of a single layer containing a material that generates electrons and holes. EL element.   The organic EL element according to claim 1, wherein a work function of the hole receiving electrode is 4.0 eV or more.   4. The organic EL device according to claim 1, wherein a difference between an ionization potential (Ip) and an electron affinity (Ea) of the ambipolar charge generation layer is 2.5 eV or less.   The organic EL device according to claim 1, wherein the organic semiconductor is fullerene or a fullerene derivative. A first charge generation promoting layer between the light emitting layer and the ambipolar charge generation layer, and / or a second charge generation promotion layer between the ambipolar charge generation layer and the hole receiving electrode , The first charge generation promotion layer is formed of any one of LiF, MgF ₂ , and Li ₂ O, and the second charge generation promotion layer is formed of any of MoO ₃ , V ₂ O ₅ , and HAT-CN. The organic EL element according to claim 1. Anode, hole injection layer, a hole transport layer, light emitting layer, both polar charge generating layer are laminated in this order of the hole-receiving electrode, the bipolar charge generation layer and the light emitting layer in the case of having the first charge-generation promoting layer When the first charge generation promoting layer is disposed between the two charge generation promoting layers, the second charge generation promoting layer is disposed between the bipolar charge generating layer and the hole receiving electrode. arranged organic EL device according to claim 6, wherein Rukoto. A method for producing an organic EL device in which an organic functional layer including at least one light emitting layer is disposed between a first electrode and a second electrode,
By forming a bipolar charge generation layer for generating electrons and holes in one of the layers constituting the organic functional layer, one of the first and second electrodes serves as a hole receiving electrode, and the hole receiving electrode Forming the bipolar charge generation layer between the light emitting layer and the light emitting layer,
The material for forming the ambipolar charge generation layer includes an organic semiconductor in which a light emitting region is formed by changing from the end side to the ambipolarity by oxygen contained in the atmosphere around the device , and using the material under vacuum A method for producing an organic EL element, wherein after forming a film, the film is exposed to a gas containing oxygen or is supplied with a gas containing oxygen to form an ambipolar charge generation layer. The method for manufacturing an organic EL element according to claim 8 , wherein the element is sealed after the organic semiconductor has changed to bipolar at least over the entire light emitting region.